U.S. patent number 6,160,066 [Application Number 09/243,722] was granted by the patent office on 2000-12-12 for monocyclopentadienyl metal compounds for ethylene-.alpha.-olefin-copolymer production catalysts.
This patent grant is currently assigned to Exxon Chemical Patents, Inc.. Invention is credited to Jo Ann Marie Canich.
United States Patent |
6,160,066 |
Canich |
December 12, 2000 |
Monocyclopentadienyl metal compounds for
ethylene-.alpha.-olefin-copolymer production catalysts
Abstract
Described are certain monocyclopentadienyl Group IV B metal
compounds, catalyst systems comprising such monocyclopentadienyl
metal compounds and an activator, and a process using such catalyst
systems for the production of polyolefins, particularly high
molecular weight ethylene-.alpha.-olefin copolymers having a high
level of .alpha.-olefin incorporation.
Inventors: |
Canich; Jo Ann Marie (Webster,
TX) |
Assignee: |
Exxon Chemical Patents, Inc.
(Baytown, TX)
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Family
ID: |
27500856 |
Appl.
No.: |
09/243,722 |
Filed: |
February 3, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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487255 |
Jun 6, 1995 |
5955625 |
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412810 |
Mar 29, 1995 |
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265533 |
Jun 24, 1994 |
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466547 |
Jun 6, 1995 |
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Current U.S.
Class: |
526/160; 502/152;
502/155; 526/127; 526/161; 526/348; 526/352; 526/943 |
Current CPC
Class: |
C07F
17/00 (20130101); C08F 10/00 (20130101); C08F
10/00 (20130101); C08F 4/65916 (20130101); C08F
10/00 (20130101); C08F 4/6592 (20130101); C08F
4/65908 (20130101); C08F 4/65912 (20130101); C08F
4/6592 (20130101); C08F 210/16 (20130101); C08L
23/0815 (20130101); C08F 210/16 (20130101); C08F
210/14 (20130101); C08F 2500/12 (20130101); C08F
2500/18 (20130101); C08F 2500/24 (20130101); Y10S
526/943 (20130101) |
Current International
Class: |
C07F
17/00 (20060101); C08F 10/00 (20060101); C08F
4/00 (20060101); C08F 4/6592 (20060101); C08F
4/659 (20060101); C08F 210/00 (20060101); C08F
210/16 (20060101); C08F 004/00 () |
Field of
Search: |
;526/127,160,943,352,348
;502/152,155 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 416 815 A2 |
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Mar 1991 |
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EP |
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0 561 476 A1 |
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Sep 1993 |
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EP |
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WO 94/07928 |
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Apr 1994 |
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WO |
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Primary Examiner: Wu; David W.
Assistant Examiner: Choi; Ling-Siu
Attorney, Agent or Firm: Muller; William G.
Parent Case Text
This is a division of U.S. Ser. No. 08/487,255, filed Jun. 6, 1995,
U.S. Pat. No. 5,955,825; which is a continuation of U.S. Ser. No.
08/412,810 filed Mar. 29, 1995; abandoned, which is a
continuation-in-part of 08/265,533 filed Jun. 24, 1994, abandoned,
which is a C-I-P of Ser. No. 08/466,547 filed Jun. 6, 1995,
abandoned.
Claims
What is claimed is:
1. A method for producing homopolymers of ethylene or copolymers of
ethylene and olefins, comprising contacting ethylene and,
optionally, one or more of C.sub.3 -C.sub.20 olefins and C.sub.4
-C.sub.20 diolefins, with a catalyst system prepared by
combining:
a) a compound of the formula: ##STR7## wherein:
M is Zr, Hf or Ti;
(C.sub.5 H.sub.4-x R.sub.x) is a cyclopentadienyl ring which is
substituted with from zero to four substituent groups R, "x" is 0,
1, 2, 3, or 4 denoting the degree of substitution, and each
substituent group R is, independently, a radical selected from the
group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals;
substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or
more hydrogen atoms is replaced by a halogen radical, an amido
radical, a phosphido radical, an alkoxy radical, or an aryloxy
radical; C.sub.1 -C.sub.20 hydrocarbyl-substituted metalloid
radicals wherein the metalloid is selected from Group IV A of the
Periodic Table of Elements; halogen radicals; amido radicals;
phosphido radicals; alkoxy radicals; aryloxy radicals; and
alkylborido radicals; or (C.sub.5 H.sub.4-x R.sub.x) is a
cyclopentadienyl ring in which at least two adjacent R-groups are
joined together and along with the carbon atoms to which they are
attached form a C.sub.4- C.sub.20 ring system;
R' is a radical selected from the group consisting of C.sub.4-
C.sub.30 alicyclic hydrocarbyl radicals wherein one or more
hydrogen atoms may be replaced by radicals selected from the group
consisting of halogen, amido, phosphido, alkoxy, aryloxy and any
other radical containing a Lewis acidic or basic functionality,
with the proviso that R' is covalently bonded to the nitrogen atom
through a tertiary carbon atom;
each Q is independently selected from the group consisting of
univalent anionic ligands, both Q together may be an alkylidene or
a cyclometallated hydrocarbyl or a divalent anionic chelating
ligand; with the proviso that where any Q is a hydrocarbyl such Q
is not a substituted or unsubstituted cyclopentadienyl radical;
T is a covalent bridging group containing a Group IV A or V A
element;
L is a neutral Lewis base which is optionally covalently bonded to
one or both Q;
"w" is a number from 0 to 3; and
M' has the same meaning as M, and Q' has the same meaning as Q;
and,
b) an activator.
2. The method of claim 1 wherein said olefins include
.alpha.-olefins, cyclic olefins, and styrene.
3. The method of claim 2 wherein said .alpha.-olefins have 3 to 10
carbon atoms.
4. The method of claim 1 wherein M is Ti.
5. The method of claim 1 for producing an ethylene-.alpha.-olefin
copolymer of greater than 20 wt. % .alpha.-olefin content,
comprising the steps of:
(a) supplying ethylene and a liquid .alpha.-olefin to a reaction
zone at a molar ratio of .alpha.-olefin to ethylene of less than
2:1 in an amount sufficient to maintain a pressure, within the
reaction zone of from about 0.019 to about 50,000 psia; and
(b) introducing into contact with the ethylene and .alpha.-olefin
in the reaction zone said catalyst system.
6. The method of claim 1 for producing an ethylene-.alpha.-olefin
copolymer of greater than 20 wt. % .alpha.-olefin content,
comprising the steps of:
(a) supplying ethylene and an .alpha.-olefin to a reaction zone at
a molar ratio of .alpha.-olefin to ethylene of less than 2:1 in an
amount sufficient to maintain a pressure within the reaction zone
of from about 0.019 to about 50,000 psia; and
(b) introducing into contact with the ethylene and .alpha.-olefin
in the reaction zone said catalyst system;
said catalyst system being introduced in an amount sufficient to
maintain a temperature within the reaction zone of from about -100
to about 300.degree. C.
7. The method of claim 1 wherein the activator is a
non-coordinating compatible anion and Q is selected from hydride
and substituted and unsubstituted C.sub.1 -C.sub.20 hydrocarbyl
radicals.
8. The method of claim 1 wherein the activator is an alumoxane.
Description
FIELD OF THE INVENTION
This invention relates to certain monocyclopentadienyl metal
compounds, to certain catalyst systems comprising such
monocyclopentadienyl metal compounds along with an activator, and
to a process using such catalyst systems for production of
polyolefins, particularly high molecular weight
ethylene-.alpha.-olefin copolymers having a high level of
.alpha.-olefin comonomer incorporation.
BACKGROUND OF THE INVENTION
As is well known, various processes and catalysts exist for
homopolymerization or copolymerization of olefins. For many
applications it is of primary importance for a polyolefin to have a
high weight average molecular weight while having a relatively
narrow molecular weight distribution. A high weight average
molecular weight, when accompanied by a narrow molecular weight
distribution, provides a polyolefin or an ethylene-.alpha.-olefin
copolymer with high strength properties.
U.S. Pat. No. 5,264,504 discloses certain monocyclopentadienyl
metal compounds having an amido radical with an aliphatic or
alicyclic hydrocarbyl moiety attached thereto through a primary or
secondary carbon atom. EPO 416,815 discloses certain
monocyclopentadienyl metal compounds which are activated with an
alumoxane co-catalyst. U.S. Pat. No. 5,064,802 discloses certain
monocyclopentadienyl metal compounds which are activated with a
non-coordinating compatible anion of a Bronsted acid salt.
SUMMARY OF THE INVENTION
The present invention is directed to certain monocyclopentadienyl
compounds and to catalyst systems which include such
monocyclopentadienyl metal compounds along with an activator
component. The catalyst systems of the present invention are highly
productive for polymerizing ethylene and olefins to produce high
molecular weight copolymers having a high content of .alpha.-olefin
comonomer. More particularly, the present invention relates to
certain monocyclopentadienyl metal compounds which include an amido
moiety having an alicyclic hydrocarbyl moiety covalently bonded
thereto through a tertiary carbon atom. A tertiary carbon atom is
defined here as a carbon atom bonded to three other non-hydrogen
atoms.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to the discovery of certain
monocyclopentadienyl metal compounds which, by reason of the
presence therein of ligands of a particular nature, are
particularly useful in catalyst systems to provide greatly improved
performance characteristics. The monocyclopentadienyl metal
compounds of the present invention are represented by the formula:
##STR1## wherein: M is Zr, Hf or Ti;
(C.sub.5 H.sub.4-x R.sub.x) is a cyclopentadienyl ring which is
substituted with from zero to four substituent groups R, "x" is 0,
1, 2, 3, or 4 denoting the degree of substitution, and each
substituent group R is, independently, a radical selected from
C.sub.1 -C.sub.20 hydrocarbyl radicals, substituted C.sub.1
-C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms
is replaced by a halogen radical, an amido radical, a phosphido
radical, an alkoxy radical, an aryloxy radical or any other radical
containing a Lewis acidic or basic functionality; C.sub.1 -C.sub.20
hydrocarbyl-substituted metalloid radicals wherein the metalloid is
selected from the Group IV A of the Periodic Table of Elements;
halogen radicals; amido radicals; phosphido radicals; alkoxy
radicals; alkylborido radicals; or any other radical containing
Lewis acidic or basic functionality; or (C.sub.5 H.sub.4-x R.sub.x)
is a cyclopentadienyl ring in which at least two adjacent R-groups
are joined together and along with the carbon atoms to which they
are attached form a C.sub.4 -C.sub.20 ring system;
R' is a radical selected from C.sub.4 -C.sub.30, preferably C.sub.4
-C.sub.20, alicyclic hydrocarbyl radicals wherein one or more
hydrogen atoms may be replaced by radicals containing Lewis acidic
or basic functionalities such as, for example, radicals selected
from halogen, amido, phosphido, alkoxy, aryloxy and the like, with
the proviso that R' is covalently bonded to the nitrogen atom
through a tertiary carbon atom;
each Q is independently a radical selected from halide; hydride;
substituted or unsubstituted C.sub.1 -C.sub.20 hydrocarbyl;
alkoxide; aryloxide; amide; or phospide; or both Q together may be
an alkylidene or a cyclometallated hydrocarbyl or any other
divalent anionic chelating ligand, with the proviso that where any
Q is a hydrocarbyl radical, such Q is not a substituted or
unsubstituted cyclopentadienyl radical;
T is a covalent bridging group containing a Group IV A or V A
element such as, but not limited to, a dialkyl, dialicyclyl,
alkylalicyclyl, arylalicyclyl, alkylaryl or diaryl silicon or
germanium radical; alkyl and/or aryl phosphine or amine radical; or
a substituted or unsubstituted hydrocarbyl radical such as
methylene, ethylene and the like which may be substituted with
substituents selected from alkyl, alicyclyl and aryl radicals or
combinations thereof having from 1 to 20 carbon atoms and silyl
atoms.
Such compounds can also include an L.sub.w complexed thereto
wherein L is a neutral Lewis base. Examples of such neutral Lewis
bases include but are not limited to diethylether,
tetraethylammonium chloride, tetrahydrofuran, dimethylaniline,
aniline, trimethylphosphine, n-butylamine, and the like. The "w" is
a number from 0 to 3. Optionally, L may be covalently bonded to one
or both Q provided Q is not hydride or halide.
L can also be a second transition metal compound of the same type
such that the two metal centers M and M' are bridged by Q and Q',
wherein M' has the same meaning as M, and Q' has the same meaning
as Q. Such dimeric compounds are represented by the formula:
##STR2##
A preferred class of compounds of the present invention are
represented by the formula: ##STR3## wherein:
M is selected from Ti, Hf and Zr;
(C.sub.5 H.sub.4-x R.sub.x) is as defined above with respect to
Formula I;
each of R.sup.1 and R.sup.2 are independently selected from C.sub.1
-C.sub.20 hydrocarbyl radicals, and may optionally be joined
together to form a cyclic ring structure;
T is Si or Ge;
each Q is independently selected from halide, hydride, substituted
or unsubstituted C.sub.1 -C.sub.20 hydrocarbyl radicals; alkoxide;
amide; and phosphide radicals, with the proviso that Q is not a
substituted or unsubstituted cyclopentadienyl radical;
R' is selected from C.sub.4 -C.sub.20 alicyclic hydrocarbyl
radicals with the proviso that R' is covalently bonded to the
nitrogen atom through a tertiary carbon atom; and
L.sub.w is optional and is as defined above.
A more preferred class of compounds of the present invention are
those compounds represented by Formula IV: ##STR4##
wherein:
M is selected from Ti, Zr and Hf;
T is selected from Si or Ge;
each of R.sup.1 and R.sup.2 is independently selected from C.sub.1
-C.sub.20 alkyl, C.sub.6 C.sub.22 aryl, C.sub.3 -C.sub.20
cycloalkyl radicals or combinations thereof and may optionally be
joined together to form a cyclic ring structure;
each R.sup.3 is independently selected from hydrogen; C.sub.1
-C.sub.20 alkyl; C.sub.3 -C.sub.20 cycloalkyl; C.sub.6 -C.sub.22
aryl; halogen; amido; phosphido; alkoxy; aryloxy; alkylborido; and
the like radicals; or combinations thereof;
each Q is independently selected from hydrogen; halogen; C.sub.1
-C.sub.20 alkyl; C.sub.6 -C.sub.22 aryl; C.sub.3 -C.sub.20
cycloalkyl; alkoxy; aryloxy; amido; and phosphido radicals or
combinations thereof;
u is an integer of from 0 to 6, preferably 0 to 4, such as from 1
to 3;
x is 0-4;
each R.sup.4 is independently selected from hydrogen; halogen,
C.sub.1 -C.sub.10 alkyl; C.sub.3 -C.sub.10 cycloalkyl; C.sub.6
-C.sub.22 aryl; amido; alkoxy; aryloxy; or combinations thereof and
the like radicals; or two R.sup.4 groups along with the carbon atom
or atoms to which they are attached, form a saturated or partially
saturated alicyclic group or form an aryl group; and
Lw is optional and is as defined above.
Preferred compounds within the scope of Formula IV are those
wherein each R.sup.3 is independently selected from C.sub.1
-C.sub.20 alkyl; C.sub.3 -C.sub.20 cycloalkyl; C.sub.6 -C.sub.22
aryl; or combinations thereof; and M is titanium. As utilized
herein, the term "alkyl", alone or in combination, means a
straight-chain or branched-chain alkyl radical containing from 1 to
about 20, preferably from 1 to about 10 carbon atoms. Examples of
such radicals include methyl, ethyl, n-propyl, iso-propyl, n-butyl,
iso-butyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl,
decyl, dodecyl, and the like. Such alkyl and alicyclic radicals may
carry one or more substitutes selected from alkoxy, halo, aryloxy,
hydroxy, amino, phosphino, borido, nitro and the like. The term
"alkoxy", alone or in combination means an alkyl oxy radical
wherein the term "alkyl" is as defined above. Examples of suitable
alkoxy radicals include methoxy, ethoxy, n-proxy, iso-propoxy,
n-butoxy, sec-butoxy, tert-butoxy, pentoxy and the like. The term
"alicyclic", alone or in combination, means a branched or
unbranched cyclic alkyl radical as defined above which is
saturated, or partially saturated. Examples of such alicyclic
radicals include cyclopropyl, cyclobutyl, cyclohexyl, cyclododecyl,
2-methylcyclohexyl, norbornyl, adamantyl and the like. The term
"aryl", alone or in combination, means a mono, bi or poly aromatic
radical. Examples of such radicals include phenyl,
cycloheptatrienyl, naphthyl, anthracenyl, chrysenyl, azulenyl,
biphenyl, p-terphenyl, 1-phenyl naphethyl and the like. Such aryl
radicals may carry one or more substituents selected from alkyl,
alkoxy, aryloxy, halogen, hydroxy, amino, phosphido, borido, nitro
and the like. Examples of such substituted aryl radicals include
p-tolyl, 4-methoxyphenyl, 4t-butylphenyl and the like. The term
"aryloxy", alone or in combination, means an aryl oxy radical
wherein aryl is as defined above. Examples include phenoxy and the
like. The term "halogen" or "halo" means fluoride, chloride,
bromide or iodide radicals. The term "ring system" means a bi- or
polycyclic system wherein one or more aromatic radicals is fused to
one or more alicyclic and/or aryl radicals. Examples of such ring
systems include fluorenyl, indenyl, tetrahydroindenyl, benzindenyl,
and the like which systems may be substituted with one or more
radicals such as alkyl radicals.
A tertiary (30) carbon atom means a carbon atom which is bonded to
three other non-hydrogen atoms. An alicyclic hydrocarbyl radical
bonded to a nitrogen atom through a tertiary carbon atom means that
the tertiary carbon atom is a member of the alicyclic radical and
is bonded to three other non-hydrogen atoms, such as to three
carbon atoms. Examples of such radicals include 1-adamantyl,
3-noradamantyl, 1-norbornyl, 1-triptycenyl,
1-tricyclo[5.2.1.0.sup.2,6 ]decyl, 4tricyclo[2.2.1.0.sup.2,6
]heptyl, and the like. The term "hydrocarbyl" means a radical
derived from a hydrocarbon. Preferred hydrocarbyl radicals are
those containing from 1-20 carbon atoms. Examples of such radicals
include alkyl, aryl, cycloalkyl radicals or combinations thereof.
Preferred radicals are C.sub.1 -C.sub.20 alkyl, C.sub.6 -C.sub.22
aryl, and C.sub.3 -C.sub.20 cycloalkyl radicals, or combinations
thereof.
A more preferred class of compounds are those compounds represented
by the above Formula IV wherein M is Ti. A most preferred class of
compounds are those represented by the above Formula IV wherein M
is Ti and wherein R.sub.1 and R.sub.2 are independently selected
from C.sub.1 -C.sub.6 alkyl radicals, C.sub.6 -C.sub.12 aryl
radicals, C.sub.3 -C.sub.12 cycloalkyl radicals, and combinations
thereof.
Examples of specific compounds within the classes of compounds
defined by Formula IV include:
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)titanium
dimethyl;
dimethylsily(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)ti
tanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titan
ium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantyl)titanium
dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyladamantyl)titani
um dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)tita
nium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-adamantylamido)tit
anium dimethyl
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyladamantylam
ido)titanium dimethyl
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)
titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium
dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)t
itanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titan
ium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7trimethyl-1-adamantylamido
)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titan
ium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium
diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)t
itanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titan
ium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titan
ium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titan
ium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)t
itanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyl
amido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)t
itanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium
diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)t
itanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titan
ium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titan
ium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium
dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)h
afnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafni
um dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafni
um dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafni
um dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)h
afnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyl
amido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)h
afnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium
dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)h
afnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafni
um dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafni
um dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium
diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)h
afnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafni
um diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafni
um diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafni
um diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)h
afnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyl
amido)hafnium diphenyl;.
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)h
afnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium
diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)h
afnium diphenyl;
diphenylsily(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafniu
m diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafni
um diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium
dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)z
irconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirco
nium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirco
nium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirco
nium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)z
irconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyl
amido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)z
irconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium
dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)z
irconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirco
nium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirco
nium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium
diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)z
irconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirco
nium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirco
nium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirco
nium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)z
irconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyl
amido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)z
irconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium
diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)z
irconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirco
nium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamid
o)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirco
nium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)titan
ium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ti
tanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ti
tanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)
titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)t
itanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)(3-noradamantanylamido)titaniu
m dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ti
tanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ti
tanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titani
um diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ti
tanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ti
tanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo
[2.2.1.0.sup.2,6 ]heptylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titani
um diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ti
tanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ti
tanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafniu
m dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ha
fnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ha
fnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ha
fnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafniu
m dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ha
fnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ha
fnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafniu
m diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ha
fnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ha
fnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ha
fnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium
diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafniu
m diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ha
fnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ha
fnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zircon
ium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zi
rconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zi
rconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconi
um dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zi
rconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zircon
ium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zi
rconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zi
rconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zircon
ium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zi
rconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zi
rconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconi
um diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zi
rconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium
diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zircon
ium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zi
rconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zi
rconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)zirconium diphenyl;
The above specific examples wherein each Q is methyl or each Q is
phenyl is prepared from the corresponding compound wherein each Q
is chloro. The dichloro (both Q are Cl) species of each of the
above compounds are also within Formula II.
Another preferred class of compounds of the present invention are
those compounds represented by the formula: ##STR5##
wherein R.sup.3, R.sup.4, Q, M, u, w, x, and L are as defined
above; wherein T is selected from radicals of the formula (CR.sup.5
R.sup.6).sub.y wherein R.sup.5 and R.sup.6 are independently
selected from hydrogen and C.sub.1 -C.sub.20 hydrocarbyl radicals;
and wherein y is 1, 2, or 3.
A more preferred class of compounds are those compounds represented
by the above Formula V wherein M is Ti. A most preferred class of
compounds are those represented by the above Formula V wherein M is
Ti and wherein R.sup.5 and R.sup.6 are independently selected from
hydrogen, C.sub.1 -C.sub.6 alkyl radicals, C.sub.6 -C.sub.12 aryl
radicals, C.sub.3 -C.sub.12 cycloalkyl radicals and combinations
thereof.
Examples of specific compounds within the class of compounds
defined by Formula V include:
methylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
methylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium
dimethyl;
methylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titan
ium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium
dimethyl;
methylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)ti
tanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium
dimethyl;
methylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titan
ium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylami
do)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)t
itanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyl
amido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)t
itanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titani
um dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamid
o)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)ti
tanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantyla
mido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)ti
tanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium
dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium
dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titani
um dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium
dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)tit
anium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium
dimethyl;
ethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2,6
]heptylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,
6 ]heptylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,
6 ]heptylmido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(4tricyclo[2.2.1.0.sup.2,
6 ]heptylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titaniu
m dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)ti
tanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantyl
amido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamid
o)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adaman
tylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamid
o)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.0.sup.2
,6 ]heptylamido)titanium dimethyl;
The above named specific compounds wherein each Q is methyl are
prepared from the corresponding compound wherein each Q is chloro.
Thus, specific compounds within Formula V are those wherein each Q
is chloro. Also, the corresponding compounds wherein each Q is
phenyl, and M is zirconium or hafnium in place of titanium and
(CR.sup.3 R.sup.4).sub.y is methylphenylmethylene,
tetramethylethylene, tetraethylethylene, propylene,
hexamethylpropylene, 1,1-dimethyl propylene,
1,1,2,2-tetramethylpropylene and the like, are also specific
compounds within the above Formula V.
The compounds of the present invention can be made using the
following general procedure and the specific examples set forth
herein.
A lithiated monocyclopentadienyl compound (C.sub.5 H.sub.5-x
R.sub.x)Li is reacted with a dihalide of a bridging compound,
R.sup.1 R.sup.2 TX.sub.2 wherein X is a halide radical, in a
suitable solvent such as tetrahydrofuran. The resulting compound is
represented by the formula (C.sub.5 H.sub.5-x R.sub.x)TR.sup.1
R.sup.2 X.
The compound (C.sub.5 H.sub.5-x R.sub.x)TR.sup.1 R.sup.2 X is then
reacted with a lithiated amido compound of the formula LiHN-R' in a
suitable solvent followed by addition of two equivalants of methyl
lithium or similar compound, and subsequent addition of a Group IV
metal compound complex such as MX.sub.4 .multidot.2Et.sub.2 O
wherein M is a metal and X is a halide. The resulting compound is
represented by the formula R.sup.1 R.sup.2 T(C.sub.5 H.sub.4-x
R.sub.x)(N-R')MX.sub.2.
The compound R.sup.1 R.sup.2 T(C.sub.5 H.sub.4-x
R.sub.x)(N-R')MX.sub.2 can be utilized as is or it can be converted
to the corresponding dihydride, dialkyl, diaryl dicycloalkyl,
dialkylaryl, dicycloalkylaryl, dialkylcycloalkyl, or mixtures
thereof and the like to utilize with an activator which is not
suitable for use when the Q ligands are halide and the like as more
fully set forth below.
Monocyclopentadienyl metal compounds of the present invention have
been discovered to produce a highly productive catalyst system
which produces an ethylene-.alpha.-olefin copolymer of
significantly greater molecular weight and .alpha.-olefin comonomer
content as compared with other species of monocyclopentadienyl
metal compounds when utilized in an otherwise identical catalyst
system under identical polymerization conditions.
All of the above-defined monocyclopentadienyl metal compounds are
useful, in combination with an activator or co-catalyst, to
polymerize .alpha.-olefins or other unsaturated hydrocarbon based
monomers including cyclic olefins. Suitable activators include
alumoxanes and activators comprising a cation and a
non-coordinating compatible anion.
The alumoxane component is an oligomeric compound which may be
represented by the general formula (R.sup.10 -Al-O).sub.m which is
a cyclic compound, or may be R.sup.11 (R.sup.12 Al-O-).sub.m
AlR.sup.13.sub.2 which is a linear compound. An alumoxane is
generally a mixture of both the linear and cyclic compounds. In the
general alumoxane formula R.sup.10, R.sup.11, R.sup.12 and R.sup.13
are, independently a C.sub.1 -C.sub.5 alkyl radical, for example,
methyl, ethyl, propyl, butyl or pentyl and "m" is an integer from 1
to about 50. Most preferably, R.sup.10, R.sup.11, R.sup.12 and
R.sup.13 are each methyl and "m" is at least 4. When an alkyl
aluminum halide is employed in the preparation of the alumoxane,
one or more R.sup.10-13 groups may be halide.
As is now well known, alumoxanes can be prepared by various
procedures. For example, a trialkyl aluminum may be reacted with
water, in the form of a moist inert organic solvent; or the
trialkyl aluminum may be contacted with a hydrated salt, such as
hydrated copper sulfate suspended in an inert organic solvent, to
yield an alumoxane. Generally, however prepared, the reaction of a
trialkyl aluminum with a limited amount of water yields a mixture
of both linear and cyclic species of alumoxane.
Suitable alumoxanes utilized in the catalyst systems of this
invention are those prepared by the hydrolysis of a
trialkylaluminum; such as trimethylaluminum, triethylaluminum,
tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride,
diisobutylaluminumchloride, diethylaluminumchloride, and the like.
The most preferred alumoxane for use is methylalumoxane (MAO).
Methylalumoxanes having an average degree of oligomerization of
from about 4 to about 25 ("m"=4 to 25), with a range of 13 to 25,
are the most preferred.
Modified alumoxanes can also be utilized. Examples of such modified
alumoxanes are those disclosed in U.S. Pat. No. 5,041,584; EP 0 516
476; and EP 0 561 476 which are incorporated herein by
reference.
Activators comprising a non-coordinating compatible anion component
are described in U.S. Pat. No. 5,198,401 which is incorporated
herein by reference. Compounds useful as the activator compound, in
the preparation of the catalyst comprise a cation, preferably a
Bronsted acid capable of donating a proton, and a compatible
non-coordinating anion containing a single coordination complex
comprising a charge-bearing metal or metalloid core which is
relatively large (bulky), capable of stabilizing the active
catalyst species (the Group IV-B cation) which is formed when the
metallocene and activator compounds are combined, and said anion is
sufficiently labile to be displaced by olefinic, diolefinic and
acetylenically unsaturated substrates or other neutral Lewis bases
such as ethers, nitrites and the like. It is well known that
reactive cations other than Bronsted acids capable of donating a
proton are also useful. Examples of such other cations include
ferrocenium triphenylcarbonium and triethylsilylinium cations. Any
metal or metalloid capable of forming a coordination complex which
is resistant to degradation by water (or other Bronsted or Lewis
Acids) may be used or contained in the anion of the second
activator compound. Suitable metals include, but are not limited
to, aluminum, gold, platinum and the like. Suitable metalloids
include, but are not limited to, boron, phosphorus, silicon and the
like.
Compounds containing anions which comprise coordination complexes
containing a single metal or metalloid atom are, of course, well
known and many, particularly compounds containing a single boron
atom in the anion portion, are available commercially. See, for
example, U.S. Pat. No. 5,278,119. In light of this, salts
containing anions comprising a coordination complex containing a
single boron atom are preferred. In general, the second activator
compounds useful in the preparation of the catalysts of this
invention may be represented by the following general formula:
wherein:
L' is a neutral Lewis base;
H is a hydrogen atom;
[L'-H] is a Bronsted acid;
M' is a metal or metalloid;
Q"'.sup.1 to Q"'.sub.n are, independently, hydride radicals,
bridged or unbridged dialkylamido radicals, alkoxide and aryloxide
radicals, hydrocarbyl and substituted hydrocarbyl radicals,
halocarbyl and substituted halocarbyl radicals, and hydrocarbyl-
and halocarbyl-substituted organometalloid radicals and any one,
but not more than one, of Q.sub.1 to Q.sub.n may be a halide
radical;
m is an integer representing the formal valence charge of M';
n is the total number of ligands Q; and
d is an integer representing the total charge on the anion.
Activator compounds comprising boron which are particularly useful
in the preparation of catalysts of this invention are represented
by the following general formula:
wherein:
L' is a neutral Lewis base;
H is a hydrogen atom;
[L'-H].sup.+ is a Bronsted acid;
B is boron in a valence state of 3.sup.+ ;
Ar.sub.1 and Ar.sub.2 are the same or different
substituted-aromatic hydrocarbon radicals and may be linked to each
other through a stable bridging group; and
X.sub.3 and X.sub.4 are, independently, hydride radicals, halide
radicals, with the proviso that only X.sub.3 or X.sub.4 will be
halide, hydrocarbyl radicals, substituted-hydrocarbyl radicals,
halocarbyl radicals, substituted-halocarbyl radicals, hydrocarbyl-
and halocarbyl-substituted organometalloid radicals, dialkylamido
radicals, and alkoxy and aryloxy radicals.
In general, Ar.sub.1 and Ar2 may, independently, be any aromatic or
substituted-aromatic hydrocarbon radical. Suitable aromatic
radicals include, but are not limited to, phenyl, naphthyl and
anthracenyl radicals. Suitable substituents on useful
substituted-aromatic hydrocarbon radicals, include, but are not
necessarily limited to, hydrocarbyl radicals, organometalloid
radicals, alkoxy radicals, alkylamido radicals, fluoro and
fluorohydrocarbyl radicals and the like such as those useful as
X.sub.3 or X.sub.4. The substituent may be ortho, meta or para,
relative to the carbon atom bonded to the boron atom. When either
or both X.sub.3 and X.sub.4 are a hydrocarbyl radical, each may be
the same or a different aromatic or substituted-aromatic radical as
are Ar.sub.1 and Ar.sub.2, or the same may be a straight or
branched alkyl, alkenyl or alkynyl radical, a cyclic hydrocarbon
radical or an alkyl-substituted cyclic hydrocarbon radical. X.sub.3
and X.sub.4 may also, independently, be alkoxy or dialkylamido
radicals, hydrocarbyl radicals and organometalloid radicals and the
like. As indicated supra, Ar.sub.1 and Ar.sub.2 may be linked to
each other. Similarly, either or both of Ar.sub.1 and Ar.sub.2
could be linked to either X.sub.3 or X.sub.4. Finally, X.sub.3 and
X.sub.4 may also be linked to each other through a suitable
bridging group.
Illustrative, but not limiting, examples of boron compounds which
may be used as an activator component in the preparation of the
improved catalysts of this invention are trialkyl-substituted
ammonium salts such as triethylammonium tetra(phenyl)boron,
tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium
tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,
trimethylammonium tetra(octolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium
tetra(o,p-dimethylphenyl)boron, tributylammonium
tetra(m,m-dimethylphenyl)boron, tributylammonium
tetra(p-trifluoromethylphenyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium
tetra(o-tolyl)boron and the like; N,N-dialkyl anilinium salts such
as N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium
tetra(phenyl)boron, N,N-2,4,6-pentamethylanilinium
tetra(phenyl)boron and the like; dialkyl ammonium salts such as
di(isopropyl)ammonium tetra(pentafluorophenyl)boron,
dicyclohexylammonium tetra(phenyl)boron, and the like; and triaryl
phosphonium salts such as triphenylphosphonium tetra(phenyl)boron,
tri(methylphenyl)phosphonium tetra(phenyl)boron,
tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like.
Similar lists of suitable compounds containing other metals and
metalloids which are useful as activator components could be made,
but such lists are not deemed necessary to a complete disclosure.
In this regard, it should be noted that the foregoing list is not
intended to be exhaustive and other boron compounds that would be
useful as well as useful compounds containing other metals or
metalloids would be readily apparent, from the foregoing general
equations, to those skilled in the art.
Also useful are neutral Lewis acid ioning activators. An example of
such activator is trisperfluorinated phenyl boron
(B[pfp].sub.3).
It is important to continued polymerization operations that either
the metal cation initially formed from the metallocene, or a
decomposition product thereof, be a relatively stable catalyst. It
is also important that the anion of the activator compound be
chemically stable and bulky. Further, when the cation of the
activator component is a Bronsted acid, it is important that the
acidity of the activator compound be sufficient, relative to the
metallocene, to facilitate the needed proton transfer. Conversely,
the basicity of the metal complex must also be sufficient to
facilitate the needed proton transfer. In general, metallocenes in
which the Q ligands can be hydrolyzed by aqueous solutions can be
considered suitable metallocenes for forming the catalysts
described herein, because water (our reference Bronsted acid) is a
weaker acid than the ammonium ions used as cation in our preferred
ion-exchange reagents. This concept allows one of ordinary skill in
the art to choose useful metallocene components because stability
to water is a basic chemical property easily determined
experimentally or by using the chemical literature.
In view of the above, when utilizing an activator comprising a
non-coordinating compatible anion, the metal component should be
one wherein each Q is selected from the group consisting of hydride
and substituted and unsubstituted hydrocarbyl radicals. Preferred Q
ligands are hydride, C.sub.1 -C.sub.12 alkyl and C.sub.6 -C.sub.12
alkaryl and silyl radicals. Most preferred are those Q ligands
selected from methyl and benzyl radicals. The preferred metal
component species for use with an activator comprising a
non-coordinating compatible anion are those set forth above wherein
each Q is methyl. Such compounds can be generated in situ by
combining a metal component wherein Q is other than a hydride or
hydrocarbyl radical with an agent, e.g., any alkylating agent, and
optionally, the activator component (e.g., an alumoxane or alkyl
aluminum).
In one embodiment of the invention, the chemical reactions which
occur upon combination of a monocyclopentadienyl metal compound
with a non-coordinating compatible anion activator compound may be
represented by reference to the general formulae set forth herein
as follows: ##STR6##
wherein v is an integer 0.gtoreq.v.gtoreq.w B' represents the anion
portion of a compatible activator corresponding to the general
formulae set forth in Equation I. When the monocyclopentadienyl
metal compound and the non-coordinating compatible anion activator
components used to prepare the improved catalysts of the present
invention are combined in a suitable solvent or diluent, all or a
part of the cation of the activator (the acidic proton) combines
with one of the substituents on the metallocene compound. In the
case where the metallocene component has a formula corresponding to
that of the general formula above, a neutral compound is liberated,
which neutral compound either remains in solution or is liberated
as a gas. In this regard, it should be noted that if either Q in
the metallocene component is a hydride, hydrogen gas may be
liberated. Similarly, if either Q is a methyl radical, methane may
be liberated as a gas. In the cases where the first component
wherein two Q form an alkylidene or cyclometalled hydrocarbyl
diradical has a formula corresponding to those of general formulae
of the reaction sequence shown directly above, the substituent on
the metal is protonated but no substituent is liberated. In
general, the rate of formation of the products in the foregoing
reaction equations will vary depending upon the choice of the
solvent, the acidity of the [L'-H].sup.+ selected, the particular
L', the anion, the temperature at which the reaction is completed
and the particular monocyclopentadienyl derivative of the metal
selected.
As indicated, the improved catalyst compositions of the present
invention will, preferably, be prepared in a suitable solvent or
diluent. Suitable solvents or diluents include any of the solvents
known in the prior art to be useful as solvents in the
polymerization of olefins, diolefins and acetylenically unsaturated
monomers. Suitable solvents, then, include, but are not necessarily
limited to, straight and branched-chain hydrocarbons such as
isobutane, butane, pentane, hexane, heptane, octane and the like;
cyclic and alicyclic hydrocarbons such as cyclohexane,
cycloheptane, methylcyclohexane, methylcycloheptane and the like
and, particularly aromatic and alkyl-substituted aromatic compounds
such as benzene, toluene, xylene and the like. Suitable solvents
also include liquid olefins which may act as monomers or comonomers
including ethylene, propylene, butadiene, cyclopentene, hexene,
3-methyl-1-pentene, 4methyl-1-pentene, 1,4-hexadiene, 1-octene,
1-decene and the like. Suitable solvents further include basic
solvents which are not generally useful as polymerization solvents
when conventional Ziegler-Natta type polymerization catalysts are
used such as chlorobenzene.
Catalysts of this invention which are highly productive may be
prepared at ratios of monocyclopentadienyl metal compound to
non-coordinating compatible anion activator of 10:1 to about 1:1,
preferably about 3:1 to 1:1.
With respect to the combination of a monocyclopentadienyl metal
compound and non-coordinating compatible anion activator compound
to form a catalyst of this invention, it should be noted that the
two compounds combined for preparation of the active catalyst must
be selected so as to avoid transfer of a fragment of the activator
compound anion, particularly an aryl group, to the
monocyclopentadienyl metal cation, thereby forming a catalytically
inactive species. When anions consisting of hydrocarbyl anions are
used, there are several means of preventing anion degradation and
formation of inactive species. One method is to carry out the
protonolysis process in the presence of small Lewis bases such as
tetrahydrofuran. Discrete complexes can be isolated from these
reactions, but the Lewis base is insufficiently labile to be
displaced readily by olefin monomers, resulting in, at best,
catalysts of very low activity. Another method of avoiding
deleterious anion degradation is by steric hindrance. Anions of the
second component which contain aryl groups can be made more
resistant to degradation by introducing substituents in the ortho
positions of the phenyl rings. While active metallocene
polymerization catalysts can be generated by this method, the
complex reaction chemistry often prevents characterization of the
catalytically active species. Steric hindrance can also result from
substitutions on the cyclopentadienyl rings of the
monocyclopentadienyl metal compound component. Hence, wherein the
mono(cyclopentadienyl) metal compound used is a
[peralkyl-substituted monocyclopentadienyl] Group IVB metal
compound, the high degree of substitution on the cyclopentadienyl
ring creates sufficient bulkiness that the Lewis base generated by
the protonolysis reaction may not coordinate to the metal. Also
polyarylborate anions without substituents on the aryl rings may
not transfer aryl fragments to generate catalytically inactive
species.
Another means of rendering the anion of the activator compound more
resistant to degradation is afforded by fluoride substitution,
especially perfluoro substitution, in the anion thereof. One class
of suitable non-coordinating anions can be represented by the
formula [B(C.sub.6 F.sub.5).sub.3 Q'"] where Q'" is a monoanionic
non-bridging radical as described above. The preferred anion of the
activator compound of this invention,
tetra(pentafluorophenyl)boron, hereafter referred to for
convenience by the notation [B(C.sub.6 F.sub.5).sub.4 ], or
[B(pfp).sub.4 ], is virtually impervious to degradation and can be
used with a much wider range of monocyclopentadienyl metal cations,
including those without substitution on the cyclopentadienyl rings,
than anions comprising hydrocarbyl radicals.
Since this anion has little or no ability to coordinate to the
monocyclopentadienyl metal cation and is not degraded by the
monocyclopentadienyl metal cation, structures of the ion-pair
catalysts using the [B(pfp).sub.4 ] anion depend on steric
hindrance of substituents on the cyclopentadienyl ring of the
substituent on the nitrogen of the amido ligand
monocyclopentadienyl metal compound, the nature of the cation of
the activator component, the Lewis base liberated from the
protonolysis reaction, and the ratio at which the
monocyclopentadienyl metal and activator component are combined.
Thus, preferred catalyst systems having a non-coordinating
compatible ion activator are those compounds of the above Formulas
IV-VI, and, specifically, those species set forth above, in
combination with [B(pfp).sub.4 ]. If Lewis bases other than that
liberated from the proton transfer process are present, they may
complex to the metal to form modified catalysts of this
invention.
Catalyst Systems
The catalyst systems employed in the method of the invention
comprise a complex formed upon admixture of the metal component
with an activator component. The catalyst system may be prepared by
addition of the requisite metal component and either one or more
alumoxane components or one or more non-coordinating anion
components, or a combination of both, to an inert solvent in which
olefin polymerization can be carried out by a solution, slurry or
bulk phase polymerization procedure. Additional co-catalysts and/or
scavenger compounds, e.g., alkyl aluminum or alkyl boron compounds,
may also be included.
The catalyst system may be conveniently prepared by placing the
selected metal component and the selected activator component, in
any order of addition, in an alkane or aromatic hydrocarbon
solvent--preferably one which is also suitable for service as a
polymerization diluent. Where the hydrocarbon solvent utilized is
also suitable for use as a polymerization diluent, the catalyst
system may be prepared in situ in the polymerization reactor.
Alternatively, the catalyst system may be separately prepared, in
concentrated form, and added to the polymerization diluent in a
reactor. Or, if desired, the components of the catalyst system may
be prepared as separate solutions and added to the polymerization
diluent in a reactor, in appropriate ratios, as is suitable for a
continuous liquid phase polymerization reaction procedure. Alkane
and aromatic hydrocarbons suitable as solvents for formation of the
catalyst system and also as a polymerization diluent are
exemplified by, but are not necessarily limited to, straight and
branched chain hydrocarbons such as isobutane, butane, pentane,
hexane, heptane, octane and the like, cyclic and alicyclic
hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,
methylcycloheptane and the like, and aromatic and alkyl-substituted
aromatic compounds such as benzene, toluene, xylene and the like.
Suitable solvents also include liquid olefins which may act as
monomers or comonomers including ethylene, propylene, 1-butene,
hexene and the like.
In accordance with this invention, when the activator is alumoxane,
optimum results are generally obtained wherein the Group IV B metal
compound is present in the polymerization diluent in a
concentration of from about 0.0001 to about 1.0 millimoles/liter of
diluent and the alumoxane component is present in an amount to
provide a molar aluminum to transition metal ratio of from about
1:1 to about 20,000:1. Where the activator is one comprising a
non-coordinating compatible anion and a cation, such activator is
present in an amount sufficient to provide a molar ratio of metal
component of from 10:1 to about 1:10. Sufficient solvent should be
employed so as to provide adequate heat transfer away from the
catalyst components during reaction and to permit good mixing.
The catalyst system ingredients--that is, the Group IV B metal
component, the activator, and polymerization diluent--can be added
to the reaction vessel rapidly or slowly. The temperature
maintained during the contact of the catalyst components can vary
widely, such as, for example, from -100.degree. to 300.degree. C.
Greater or lesser temperatures can also be employed. Preferably,
during formation of the catalyst system, the reaction is maintained
within a temperature of from about 25.degree. to 100.degree. C.,
most preferably about 25.degree. C.
Polymerization Process
A typical polymerization process of the invention comprises the
steps of contacting ethylene and a C.sub.3 -C.sub.20 olefin alone,
or with other unsaturated monomers including C.sub.3 -C.sub.20
olefins, C.sub.4 -C.sub.20 diolefins, and/or acetylenically
unsaturated monomers with a catalyst comprising, in a suitable
polymerization diluent, a monocyclopentadienyl metal compound, as
described above, and an activator. The olefin monomers include
.alpha.-olefins as well as cyclic olefins such as, for example,
cyclohexene, norborene, alkyl-substituted norborenes and the like.
For example, a catalyst comprising a monocyclopentadienyl metal
compound as described above and either 1) a non-coordinating
compatible anion activator or 2) an alumoxane activator. The
alumoxane activator is utilized in an amount to provide a molar
aluminum to titanium metal ratio of from about 1:1 to about
20,000:1 or more. The non-coordinating compatible anion activator
is utilized in an amount to provide a molar ratio of
monocyclopentadienyl metal compound to non-coordinating anion of
10:1 to about 1:10. The above reaction is conducted by reacting
such monomers in the presence of such catalyst system at a
temperature of from about -100.degree. C. to about 300.degree. C.
preferably 20.degree. C. to 250.degree. C., most preferably from
50.degree. C. to 200.degree. C. for a time of from about 1 second
to about 10 hours to produce a copolymer having a weight average
molecular weight of from about 1,000 or less to about 5,000,000,
preferably 1,000 to 1.5 million, and a molecular weight
distribution of from about 1.5 to about 15.0, preferably less than
5 and most preferably less than 4.
In a preferred embodiment of the process of this invention the
catalyst system is utilized in the liquid phase (slurry, solution,
suspension or bulk phase or combination thereof, high pressure
fluid phase or gas phase polymerization of an olefin monomer. When
utilized in a gas phase, slurry phase or suspension phase
polymerization, the catalyst systems will preferably be supported
catalyst systems. See also, for example, U.S. Pat. No. 5,057,475,
WO 94/03506, which is incorporated herein by reference. Such
catalyst systems can also be utilized in a gas phase process
without a support as described in U.S. Pat. No. 5,317,036. Such
catalyst systems can also include other well known additives such
as, for example, scavengers. See, for example, U.S. Pat. No.
5,153,157 and WO 94/07927 (Apr. 14, 1994) which are incorporated
herein by reference. These processes may be employed singularly or
in series. The liquid phase process comprises the steps of
contacting an ethylene and an olefin monomer with the catalyst
system in a suitable polymerization diluent and reacting the
monomers in the presence of the catalyst system for a time and at a
temperature sufficient to produce an ethylene-.alpha.-olefin
copolymer of high molecular weight.
The monomers for such process comprise ethylene in combination with
an .alpha.-olefin having 3 to 20 carbon atoms, preferably 3 to 10
carbon atoms, most preferably 3 to 8 carbon atoms, for the
production of an ethylene-.alpha.-olefin copolymer. It should be
appreciated that the advantages as observed in an
ethylene-.alpha.-olefin copolymer produced with a catalyst system
of this invention would also be expected to be obtained in a
copolymer of different .alpha.-olefins wherein ethylene is not used
as a monomer as viewed in comparison to a copolymer of the same or
different .alpha.-olefins produced under similar polymerization
conditions with a catalyst system which does not use a
monocyclopentadienyl Group IV B metal compound as defined herein.
Accordingly, although this invention is described with reference to
an ethylene-.alpha.-olefin copolymer and the advantages of the
defined catalyst system for the production thereof, this invention
is not to be understood to be limited to the production of an
ethylene-.alpha.-olefin copolymer, but instead the catalyst system
hereof is to be understood to be advantageous in the same respects
to the production of a copolymer composed of two or more C.sub.3 or
higher .alpha.-olefin monomers. Copolymers of higher .alpha.-olefin
such as propylene, butene, styrene or higher .alpha.-olefins,
cyclic olefins and diolefins can also be prepared. Conditions most
preferred for the homo- or copolymerization of ethylene are those
wherein ethylene is submitted to the reaction zone at pressures of
from about 0.019 psia to about 50,000 psia and the reaction
temperature is maintained at from about -100.degree. C. to about
300.degree. C. Where the activator is an alumoxane, the aluminum to
transition metal molar ratio is preferably from about 1:1 to 20,000
to 1. A more preferable range would be 1:1 to 2000:1. The reaction
time is preferably from about 10 seconds to about 4 hours.
Without limiting in any way the scope of the invention, one means
for carrying out the process of the present invention for
production of a copolymer is as follows: in a stirred-tank reactor
liquid .alpha.-olefin monomer is introduced, such as 1-butene. The
catalyst system is introduced via nozzles in either the vapor or
liquid phase. Feed ethylene gas is introduced either into the vapor
phase of the reactor, or sparged into the liquid phase as is well
known in the art. The reactor contains a liquid phase composed
substantially of liquid .alpha.-olefin comonomer, together with
dissolved ethylene gas, and a vapor phase containing vapors of all
monomers. The reactor temperature and pressure may be controlled
via reflux of vaporizing .alpha.-olefin monomer
(autorefrigeration), as well as by cooling coils, jackets, etc. The
polymerization rate is controlled by the concentration of catalyst.
The ethylene content of the polymer product is determined by the
ratio of ethylene to .alpha.-olefin comonomer in the reactor, which
is controlled by manipulating the relative feed rates of these
components to the reactor.
EXAMPLES
In the examples which illustrate the practice of the invention the
analytical techniques described below were employed for the
analysis of the resulting polyolefin products. Molecular weight
determinations for polyolefin products were made by Gel Permeation
Chromatography (GPC) according to the following technique.
Molecular weights and molecular weight distributions were measured
using a Waters 150-CV gel permeation chromatograph equipped with a
differential refractive index (DRI) detector. The system was used
at 145.degree. C. with 1,2,4-trichlorobenzene as the mobile phase.
Three Shodex (Showa Denko America, Inc.) mixed bed columns (AT-80
M/S) were used in series. This general technique is discussed in
"Liquid Chromatography of Polymers and Related Materials III", J.
Cazes editor, Marcel Dekker, 1981, p. 207, which is incorporated
herein by reference. No corrections for column spreading were
employed; however, data on generally accepted standards, e.g.
National Bureau of Standards Polyethylene 1475 demonstrated that
such corrections on Mw/Mn (=MWD) were within 0.1 units. Mw/Mn was
calculated from elution times. The numerical analyses were
performed using waters Expert Ease software package
The following examples are intended to illustrate specific
embodiments of the invention and are not intended to limit the
scope of the invention.
Experimental Section
All procedures were performed under an inert atmosphere of helium
or nitrogen. Solvent choices were often optional, for example, in
most cases, either pentane or 30-60 petroleum ether can be
interchanged. The lithiated amides were prepared from the
corresponding amines and either n-BuLi or MeLi. Published methods
for preparing LiHC.sub.5 Me.sub.4 include C. M. Fendrick et al.,
Organometallics 1984, 3, 819 and F. H. Kohler and K. H. Doll, Z.
Naturforsch 1982, 376, 144. Other lithiated substituted
cyclopentadienyl compounds are typically prepared from the
corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by
reaction of MeLi with the proper fulvene. TiCl.sub.4 was typically
used in its etherated form. The etherate can be prepared by simply
adding TiCI.sub.4 to ether and filtering off the solid product
which is then vacuum dried. TiCI.sub.4, amines, silanes,
substituted and unsubstituted cyclopentadienyl compounds or
precursors, and lithium reagents were purchased from Aldrich
Chemical Company or Petrarch Systems. Activator components were
purchased or prepared from known literature methods. The transition
metal compounds Me.sub.2 Si(Me.sub.4 C.sub.5)(N-t-Bu)TiCl.sub.2
(Compound A) and Me.sub.2 Si(Me.sub.4 C.sub.5)(N-c-C.sub.12
H.sub.23)TiCO.sub.2 (Compound C), both of which are used as
comparative examples, were prepared as described in U.S. Pat. No.
5,264,405.
Example B--Compound B
Part 1. C.sub.5 Me.sub.4 HLi(10.0 g, 0.078 mol) was slowly added to
a Me.sub.2 SiCl.sub.2 (11.5 ml, 0.095 mol, in 225 ml of
tetrahydrofuran (thf) solution). The solution was stirred for one
hour to assure a complete reaction. The solvent was then removed in
vacuo. Pentane was added to precipitate the LiCl. The mixture was
filtered through Celite and the solvent was removed from the
filtrate in vacuo. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (15.34 g,
0.071 mol) was recovered as a pale yellow liquid.
Part 2: (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.028 mol) was
diluted in -150 ml tfh. LiHN-C.sub.10 H.sub.15 (lithiated
1-adamantylamine, 4.38 g, 0.028 mol) was added and the reaction
mixture was allowed to stir for two hours. The solvent was removed
via vacuum, and .about.100 ml of ether was added. To this, 34 ml of
MeLi (.about.1.4 M in ether, 0.048 mol) was added and the reaction
mixture was stirred for three hours. The mixture was cooled to
-30.degree. C. and TiCl.sub.4 .multidot.2Et.sub.2 O (7.74g, 0.023
mol) was slowly added and the reaction mixture was allowed to stir
overnight. The solvent was removed via vacuum and pentane was
added. This mixture was filtered through Celite to remove the LiCl.
The filtrate was reduced in volume and cooled to -30.degree. C. to
induce precipitation of the product. The product was filtered off
and washed with cold pentane yielding 1.7 g (3.8 mmol) of the
yellow solid, Me.sub.2 Si(Me.sub.4 C.sub.5)(N-C.sub.10
H.sub.15)TiCl.sub.2.
Comparative Example D--Compound D
Part 1: C.sub.5 Me.sub.4 HLi (10.0 g, 0.078 mol) dissolved in 150
ml thf was reacted with Ph.sub.2 SiCl.sub.2 (19.75 g, 0.078 mol).
The solution was stirred for three hours to assure a complete
reaction. The solvent was then removed in vacuo. Petroleum ether
was added to precipitate the LiCl. The mixture was filtered through
Celite and the solvent was removed from the filtrate in vacuo.
(C.sub.5 Me.sub.4 H)SiPh.sub.2 CI (22.0 g, 0.65 mol) was recovered
as a pale yellow liquid.
Part 2: LiHN-t-Bu (1.4 g, 0.0177 mol) was slowly added to (C.sub.5
Me.sub.4 H)SiPh.sub.2 Cl (6.0 g, 0.0177 mol) in .about.100 ml of
thf. After stirring for two hours, the solvent was removed via
vacuum and replaced with .about.150 ml of ether. Assuming an 85%
yield of (C.sub.5 Me.sub.4 H)SiPh.sub.2 (HN-t-Bu) (0.015 mmol), 21
ml of 1.4 M MeLi (0.0294 mmol) was added and allowed to stir for
three hours. The solution was then chilled to -30.degree. C. and
4.93 g of TiCl.sub.4 .multidot.2Et.sub.2 O (0.0146 mol) was added.
The mixture was stirred overnight under ambient conditions.
Isolation of the product involved removing the solvent from the
reaction mixture, adding pentane and filtering the mixture to
remove the LiCl byproduct. The pentane filtrate was reduced in
volume and the solution was chilled to -30.degree. C. to induce
crystallization. The product was filtered off, washed with cold
pentane, and dried to give 1.8 g of the yellow solid, Ph.sub.2
Si(C.sub.5 Me.sub.4)(N-t-Bu)TiCl.sub.2 (3.7 mmol).
Example E--Compound E
Part 1: (C.sub.5 Me.sub.4 H)SiPh.sub.2 Cl was prepared as described
in Example D, Part 1.
Part 2: LiHN-C.sub.1 OH.sub.15 (lithiated 1-adamantylamine, 2.78 g,
0.0177 mol) was slowly added to (C.sub.5 Me.sub.4 H)SiPh.sub.2 CI
(6.0 g, 0.0177 mol) in .about.100 ml of thf. After stirring for two
hours, the solvent was removed via vacuum and replaced with
.about.150 ml of ether. Assuming an 85% yield of (C.sub.5 Me.sub.4
H)SiPh.sub.2 Cl(HN-C.sub.10 H.sub.15) (0.015 mmol), 21.4 ml of 1.4
M MeLi (0.030 mmol) was added and allowed to stir for three hours.
The solution was then chilled to -30.degree. C. and 4.79 g of
TiCl.sub.4 .multidot.2Et.sub.2 O (0.0142 mol) was added. The
mixture was stirred overnight under ambient conditions.
Isolation of the product involved removing the solvent from the
reaction mixture, adding pentane and filtering the mixture to
remove the LiCl byproduct. The pentane filtrate was reduced in
volume and the solution was chilled to -30.degree. C. to induce
crystallization. The product was filtered off, washed with cold
pentane and methylene chloride, and dried to give 3.2 g of the
mustard yellow solid, Ph.sub.2 Si(C.sub.5 Me.sub.4)(N-C.sub.10
H.sub.15)TiCl.sub.2 (5.6 mmol).
Comparative Example F--Compound F
Part 1: (C.sub.5 Me.sub.4 H)SiPh.sub.2 Cl was prepared as described
in Example D, Part 1.
Part 2: LiHN-c-C.sub.12 H.sub.23 (lithiated cyclododecylamine, 3.35
g, 0.0177 mol) was slowly added to (C.sub.5 Me.sub.4 H)SiPh.sub.2
Cl (6.0 g, 0.0177 mol) in .about.150 ml of thf. After stirring for
two hours, the solvent was removed via vacuum and replaced with
.about.150 ml of ether. Assuming an 85 % yield of (C.sub.5 Me.sub.4
H)SiPh.sub.2 Cl(HN-c-C.sub.12 H.sub.23) (0.015 mmol) 22 ml of 1.4 M
MeLi (0.031 mmol) was added and allowed to stir for three hours.
The solution was then chilled to -30.degree. C. and 4.97 g of
TiCl.sub.4 .multidot.2Et.sub.2 O (0.0147 mol) was added. The
mixture was stirred overnight under ambient conditions.
Isolation of the product involved removing the solvent from the
reaction mixture, adding pentane and filtering the mixture to
remove the LiCl byproduct. The pentane filtrate was reduced in
volume and the solution was chilled to -30.degree. C. to induce
crystallization. The product was filtered off, washed with cold
pentane, and dried to give 2.8 g of the yellow solid, Ph.sub.2
Si(C.sub.5 Me.sub.4)(N-c-C.sub.12 H.sub.23)TiCl.sub.2 (4.6
mmol).
Example G--Compound G
Part 1. t-BuC.sub.5 H4Li (10.0 g, 0.084 mol) was slowly added to a
Me.sub.2 SiCl.sub.2 (13.0 g, 0.101 mol, in 60 ml of tetrahydrofuran
solution). The solution was stirred for 2 hours to assure a
complete reaction. The solvent was then removed in vacuo. Pentane
was added to precipitate the LiCl. The mixture was filtered through
Celite and the solvent was removed from the filtrate in vacuo.
(t-BuC.sub.5 H.sub.4)SiMe.sub.2 Cl (15.9 g, 0.074 mol) was
recovered as a pale yellow liquid.
Part 2. (t-BuC.sub.5 H.sub.4)SiMe.sub.2 Cl (6.0 g, 0.028 mol) was
diluted in .about.125 ml THF. LiHN-C.sub.10 H.sub.15 (lithiated
1-adamantylamine, 4.72 g, 0.030 mol) was added and the reaction
mixture was allowed to stir for three hours. The solvent was
removed via vacuum, and .about.150 ml of ether was added. To this,
40.7 ml of MeLi (.about.1.4 M in ether, 0.057 mol) was added and
the reaction mixture was stirred for 3 hours. The mixture was
cooled to -30.degree. C. and TiCl.sub.4 .multidot.2Et.sub.2 O (9.26
g, 0.027 mol) was slowly added and the reaction mixture was allowed
to stir overnight. The solvent was removed via vacuum and pentane
was added. This mixture was filtered through Celite to remove the
LiCl. The filtrate was reduced in volume and cooled to -30.degree.
C. to induce crystallization of the product. The product was
filtered off and washed with cold pentane yielding 3.0 g (6.7 mmol)
of the yellow solid, Me.sub.2 Si(t-BUC.sub.5
H.sub.3)(N-C10H15)TiCl2.
Example H--Compound H
Me2Si(t-BuC5H3)(N-C10H15)TiMe2 was prepared by adding a
stoichiometric amount of MeLi (.about.1.4 M in ether) to
Me2Si(t-BuC5H3)(N-C10H15)TiCl2 (1.0 g, 2.24 mmol, Compound G from
Example G) suspended in pentane. The solvent was removed via vacuum
and pentane was added to precipitate the LiCl which was filtered
off. The filtrate was reduced in volume and cooled to -30.degree.
C. to precipitate the product. Me2Si(t-BuC5H3)(N-C10H15)TiMe2 (0.36
g, 0.88 mmol) was isolated.
Example I--Compound I
Me2Si(Me4C5)(N-C10H15)TiMe2 was prepared by adding a stoichiometric
amount of MeLi (.about.1.4M in ether) to
Me2Si(Me4C.sub.5)(N-C10H15)TiCl2 (1.0 g, 2.24 mmol, Compound B from
Example B) suspended in ether. The solvent was removed via vacuum
and pentane was added to precipitate the LiCl which was filtered
off. The filtrate was reduced in volume and cooled to -30 SYMBOL
176 .backslash.f "Symbol" C to precipitate the product.
Me2Si(Me4C5)(N-C10H15)TiMe2 (0.33 g, 0.81 mmol) was isolated.
Polymerization Examples 2, 4 and 6; Comparative Examples 1, 3, 5
and 7
The polymerization reactions were performed in a stirred 1 L steel
autoclave reaction vessel which was equipped to perform continuous
Ziegler Natta polymerization reactions at pressures up to 2500 bar
and temperatures up to 300.degree. C. The reaction system was
supplied with a thermocouple and pressure transducer to measure
temperature and pressure continuously, and with means to supply
continuously purified compressed ethylene and 1-butene, 1-hexene,
propylene or any other desired unsaturated comonomer. Equipment for
continuously introducing a measured flow of catalyst solution, and
equipment for rapidly venting and quenching the reaction, and of
collecting the polymer product were also a part of the reaction
system. Without the addition of a solvent, the polymerization was
performed with a 1.6 molar ratio of 1-butene to ethylene
pressurized at 1300 bar. No hydrogen was used. The catalyst
solution was prepared by mixing a specified amount of solid
transition metal component with a methylalumoxane solution further
diluted in toluene under an inert atmosphere. This catalyst
solution was continuously fed by a high pressure pump into the
reactor at a rate which resulted in the desired reactor temperature
of 180 SYMBOL 176 .backslash.f "Symbol" C. The reactor contents
were stirred at 1,000 rpm and the reactor mass flow rate used was
40 kg/hr. Exact run conditions including catalysts preparation
[transition metal component (TMC) (g), weight percent
methylalumoxane (MAO) and volume used (L), total catalyst solution
volume prepared (L), and concentration (g TMC/L) and (g MAO/L)],
catalyst feed rate (L/hr), polymer production rate (kg polymer/hr),
molar Al/M ratio, TMC productivity (kg polymer/g TMC), TMC
productivity (kg polymer/mol TMC), catalyst productivity (kg
polymer/ g catalyst) and polymer characteristics including weight
average MW (daltons), molecular weight distribution (Mw/Mn=MWD),
melt index (g/10 minutes at 190 SYMBOL 176 .backslash.f "Symbol"
C), weight percent comonomer (determined by 1H NMR), and "catalyst
reactivity ratios" (r1) are collected in Table 1. "Catalyst
reativity ratios" were calculated as (1-butene/ethylene molar ratio
in reactor-feed) x (ethylene/1-butene molar ratio in the polymer).
An example of how to use the information contained in Table 1
follows using Example 1.
Using the reactor design as described above, and using a molar
ratio of 1-butene to ethylene of 1.6 without the addition of a
solvent, the temperature of the cleaned reactor containing ethylene
and 1-butene was equilibrated at the desired reaction temperature
of 180 SYMBOL 176 .backslash.f "Symbol" C. The catalyst solution
was prepared by mixing 0.878 g of solid compound A with 0.75 L of a
30 weight percent methylalumoxane solution with added toluene to
give a total volume of 10L. This catalyst solution was continuously
fed by a high pressure pump into the reactor at a rate of 0.84 L/hr
which resulted in a temperature of 180 SYMBOL 176 .backslash.f
"Symbol" C in the reactor. During this run, ethylene and 1-butene
were pressured into the autoclave at a total pressure of 1300 bar.
The reactor contents were stirred at 1,000 rpm, and the mass flow
rate through the reactor was 40 kg/hr. The yield of polymer product
was 4.3 kg/hr of an ethylene-1-butene copolymer which had a weight
average molecular weight of 61,000 daltons, a molecular weight
distribution of 3.346, and a comonomer incorporation of 32.4 weight
percent butene measured by H NMR. The polymer melt index measured
at 190 SYMBOL 176 .backslash.f "Symbol" C was 6.6 g/10 minutes. The
catalyst reactivity ratio of ethylene to butene was calculated to
be 6.7. Productivities were calculated at 59 kg polymer/g A, 21,600
kg polymer/mol A, and 0.26 kg polymer/g catalyst.
EXAMPLE G: Ionic Invention Catalyst and Polymerization of Cyclic
Olefin Copolymer
Me2Si(t-BuCp)(N-C10H15)TiMe2 (40.0 mg) (compound G) was weighed out
under inert atmosphere and N,N-Dimethylanalinium
tetrakis-perfluorophenyl boron, [(DMAH)] [B(pfp)4], activator was
added to give a slight molar excess of the transition metal
complex. Dry toluene (2 mL) was added by pipette and the mixture
allowed to stand with occasional stirring until activation was
complete (10 to 20 min.). The resulting mixture was septa sealed
and ready for transfer to the reactor via cannula.
Dry toluene (0.8 liter) was transferred to a clean, dry and N2
purged 2 liter autoclave reactor using air sensitive technique. The
solvent was stirred under a continued slow N2 purge while the
reactor was equilibrated at 60.degree. C. Triisobutylaluminum
(TIBA) was added as a scavenger by diluting 0.5 mL of a 1 M
solution in toluene with additional toluene (10 to 20 mL) and
transferring to the reactor via cannula through the purge port
using standard air sensitive technique. Norbornene (53 g) was added
to the reactor as a concentrated solution in toluene (86 wt. %) via
cannula through the purge port using standard air sensitive
technique. The N2 purge was shut off simultaneously as the reactor
was sealed. Ethylene gas (1 bar) was added to the reactor until the
solution was saturated. (Molar feed ratio
Norbornene:Ethylene=3.9:1.) The ethylene regulator and flow
controller were set to maintain the 15 psig ethylene pressure with
a replenishing flow. The reactor was then quickly vented and 18.0 g
of the pre-activated catalyst was added to the reactor via cannula
through the purge port. The port was then sealed and the ethylene
pressure quickly returned to 15 psig by opening the flow
controller. The mixture was stirred at 60.degree. C. for 20
minutes.
The reaction was quenched by rapid venting of the rector and its
contents poured into one liter of rapidly stirring acetone. The
resulting white solid polymer was washed, separated by filtration,
and dried in a vacuum oven overnight (60.degree. C., -30 in. Hg).
Copolymer (24.2 g) was obtained that had a glass transition
temperature of 85.degree. C., Mw=1,380,000, MWD=1.42.
TABLE 1
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MAO Total Feed Production TMC TMC Catalyst Wt. TMC (Wt. MAO Vol TMC
MAO Rate Rate Al/M Prod Prod Prod MW % No TMC (g) %) (L) (L) (g/L)
(g/L) (L/hr) (kg/hr) (molar) (kg/g) (kg/mol) (kg/g) MW D MI C4
__________________________________________________________________________
r1 C1 A 0.878 30 0.75 10 0.0878 19.6 0.84 4.3 1416 59 21,601 0.26
61,000 3.346 6.6 32.4 6.7 2 B 0.765 30 0.60 8 0.0956 19.6 0.46 3.4
1575 76 33,996 0.37 88,700 3.166 2.2 34.2 6.2 C3 C 1.532 30 1.00 20
0.0766 13.1 1.61 5.4 1405 43 20,757 0.25 76,800 2.858 6.0 40.0 4.8
4 C 0.513 30 0.33 10 0.0513 8.6 1.59 4.1 1385 50 23,758 0.29 81,800
2.967 4.7 41.1 4.6 C5 D 1.080 30 0.70 11 0.0982 16.6 1.42 4.1 1437
29 14,307 0.17 59,100 3.617 7.2 38.6 5.1 6 F 1.801 30 1.00 18
0.1001 14.5 1.15 5.0 1426 43 24,792 0.30 66,500 3.280 8.1 36.0 5.7
C7 F 1.547 30 0.80 10 0.1547 20.9 1.72 4.4 1402 16 9,880 0.12
72,600 2.825 8.3 42.4
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4.3
* * * * *